Process for the selective absorption of chlorine from CO2 -containing off-gases

ABSTRACT

The invention provides a process for the selective absorption of chlorine from CO2-containing off-gases, which comprises washing the off-gases with an aqueous solution which contains 0.1-10% by weight of NaHCO3 and 0.01-5% by weight of NaHSO3.

The combustion of chlorinated hydrocarbons gives according to the DEACON equilibrium, besides hydrogen chloride and CO₂, also elemental chlorine. This chlorine is not allowed to be discharged into the environment and must therefore be removed from the off-gas to the greatest possible extent. In the Federal Republic of Germany, the chlorine concentration must be below 5 mg/m³.

The absorption of chlorine from gas streams has hitherto generally been carried out using sodium hydroxide solution with the formation of sodium hypochlorite:

    Cl.sub.2 +2NaOH→NaCl+NaOCl+H.sub.2 O

In the case of gas streams which besides chlorine contain only inert gases, an industrially useful product (NaOCl solution) is obtained from the absorbent. However, if the off-gas which is to be absorbed contains besides Cl₂ other alkali-soluble gases, the identical procedure gives a solution of several salts which is virtually unusable. For example, CO₂ is also absorbed by sodium hydroxide solution with the formation of NaHCO₃ :

    NaOH+CO.sub.2 →NaHCO.sub.3

According to the prior art, NaOCl is removed from these mixtures of salts by adding Na₂ SO₂.

The minimization of the troublesome simultaneous absorption of CO₂ has already received much attention, so that techniques are already known for specific applications.

A process described in DE-A-2,849,498 employs two absorption cycles running on NaOH for absorbing Cl₂ to give NaCl and NaOCl. A portion of the resulting NaOCl is continually discharged and decomposed using NaHSO₃. However, the off-gas purified by this process still contains about 10 ppm, i.e. about 30 mg/m³, of chlorine.

The multistage countercurrent absorption of chlorine using sodium hydroxide solution which is described in U.S. Pat. No. 3,984,523 is suitable only for gas streams which firstly are highly laden with chlorine and secondly contain CO₂ in a concentration similar to that of Cl₂. However, owing to the high absorption of CO₂ in alkali, this process is not suitable for use with a 100-1000-fold excess of CO₂ relative to Cl₂ in the off-gas. If the off-gas is highly laden with chlorine, the CO₂ which has been absorbed in the last stage is driven off again in the first stage by chlorine, a procedure which is not possible at low chlorine loadings. Furthermore, U.S. Pat. No. 3,984,523 states that it is not possible to achieve a chlorine content in the off-gas lower than 5 mg/m³ of Cl₂ by washing with NaHCO₃ solution.

Surprisingly, it has now been found that using a NaHCO₃ solution to which small amounts of NaHSO₃ are added, it is possible to remove virtually all the Cl₂, even when the washing solution is repeatedly reused, without CO₂ being absorbed. The concentrations of Cl₂ achieved in the purified gas were below the analytical limit of detection.

The present invention accordingly provides a process for the selective absorption of chlorine from CO₂ -containing off-gas, which comprises washing the off-gas with an aqueous solution which contains 0.1-10% by weight of NaHCO₃ and 0.01-5% by weight of NaHSO₃. The aqueous solution with which the off-gas is washed preferably contains 0.5-7% by weight of NaHCO₃ and 0.05-1% by weight of NaHSO₃, in particular 1-5% by weight of NaHCO₃ and 0.1- 0.5% by weight of NaHSO₃.

Instead of NaHCO₃, it is also possible to add NaOH to the washing solution since this reacts immediately with the CO₂ of the off-gas to give NaHCO₃. If the off-gas contains SO₂, it is similarly possible to add NaOH to the washing solution instead of NaHSO3, since NaOH reacts with the SO₂ to give NaHSO₃.

The process according to the invention allows high salt concentrations to be maintained in the circulated washing solution. Consequently, spent washing solution needs to be replaced by fresh washing solution at only a very low rate.

The absorption of chlorine from CO₂ -containing off-gases (flue gases) is carried out continuously in a single stage or multistage absorption plant (column, jet scrubber, etc.).

The process according to the invention can be operated so that the amount of fresh absorption solution added is sufficient to hold the pH approximately constant.

The process according to the invention is suitable in particular for CO₂ -rich gases, e.g. gases in which the CO₂ :Cl₂ ratio, by volume, ranges from about 100 to 10⁶. Thus, this invention is suitable even for those gases whose CO₂ content is 10⁴ to 10⁶ times higher than the Cl₂ content.

The invention is explained in the examples which follow.

EXAMPLE 1

A jet scrubber was used to purify 1.8 m³ /h of an off-gas which contained 70 mg/m³ of Cl₂, 20% by volume of CO₂ and 4% of O₂, the remainder being N₂.

In the steady state, the washing solution contained, besides water:

    ______________________________________                                         1. NaHCO.sub.3       4% by weight                                              2. NaHSO.sub.3     0.4% by weight                                              3. Na.sub.2 SO.sub.4                                                                              0.3% by weight                                              4. NaCl            0.2% by weight                                              ______________________________________                                    

100 ml of washing solution per hour was withdrawn and replaced by fresh washing solution. Besides water, the fresh washing solution contained:

    ______________________________________                                         1. NaHCO.sub.3     4.3% by weight                                              2. NaHSO.sub.3     0.6% by weight                                              ______________________________________                                    

The hold-up in the jet scrubber was about 8 1, and the circulated amount of washing solution was about 35 l/h. This corresponds to a ratio of gas:liquid of about 50:1. The concentration of chlorine in the purified off-gas at the outlet from the scrubber was less than 0.1 mg of Cl₂ /m³ of gas. The chlorine concentration was determined by the methyl orange method (VDI handbook "Reinhaltung der Luft", Volume 5, Register 9, VDI Guideline 3488, Part I).

EXAMPLE 2

A jet scrubber was used to purify 1.8 m³ /h of an off-gas which contained, besides N₂, 130 mg/m³ of chlorine, 20% by volume of CO₂ and 4% of O₂. In the steady state, the washing solution contained, besides water:

    ______________________________________                                         1. NaHCO.sub.3       4% by weight                                              2. NaHSO.sub.3     0.4% by weight                                              3. Na.sub.2 SO.sub.4                                                                              0.5% by weight                                              4. NaCl            0.4% by weight                                              ______________________________________                                    

100 ml of washing solution per hour was withdrawn and replaced by fresh washing solution. Besides water, the fresh washing solution contained:

    ______________________________________                                         1. NaHCO.sub.3       5% by weight                                              2. NaHSO.sub.3     0.8% by weight                                              ______________________________________                                    

In other respects, the procedure of Example 1 was followed.

The concentration of chlorine in the purified off-gas at the outlet from the scrubber was less than 0.1 mg of Cl₂ /m³ of gas. 

We claim:
 1. A process for the selective absorption of chlorine from CO₂ -containing off-gas, which comprises treating an off-gas wherein the amount of chlorine in the off-gas exceeds 5 mg per m³ of off-gas but the CO₂ :Cl₂ ratio, by volume, ranges in the off-gas from about 100 to 10⁶, wherein the treatment comprises:washing said off-gas in a single-stage absorption zone with a circulating, repeatedly re-used, aqueous washing solution, which solution contains 0.1-10% by weight of NaHCO₃ and 0.01-5% by weight of NaHSO₃ and in which the amount of NaHSO₃ is smaller than the amount of NaHCO₃, thereby selectively absorbing chlorine substantially without absorbing carbon dioxide, and obtaining from the single-stage absorption zone an off-gas containing less than 5 mg of chlorine per m³ of gas.
 2. The process as claimed in claim 1, wherein the CO₂ content is 10⁴ to 10⁶ times higher than the Cl₂ content.
 3. The process as claimed in claim 1, wherein the off-gas is washed with an aqueous solution which contains 0.5%-7% by weight of NaHCO₃ and 0.05%-1% by weight of NaHSO₃.
 4. The process as claimed in claim 1, wherein the off-gas is washed with an aqueous solution which contains 1%-5% by weight of NaHCO₃ and 0.1%-0.5% by weight of NaHSO₃.
 5. The process as claimed in claim 1, wherein the circulating, repeatedly-reused washing solution contains, besides water, NaHCO₃, and NaHSO₃, circulating amounts of Na₂ SO₄ and NaCl.
 6. The process as claimed in claim 1, wherein said off-gas is a flue gas.
 7. The process as claimed in claim 1, wherein fresh absorption solution is added to the circulating, repeatedly-reused washing solution, in an amount sufficient to hold the pH of the circulating, repeatedly-reused washing solution approximately constant. 